Production of ammonium betaines

ABSTRACT

The production of ammonium betaines by reaction of adducts of an oxide of sulfur and an amine with an aziridine, and the new ammonium betaines themselves. The new compounds obtainable according to the process of the invention are surfactants, particularly detergents and assistants in the textile field, softeners, washing aftertreatment agents, germicides, and valuable starting materials for the production of detergents, cleaning agents, detergents, wetting agents, textile assistants, dishwashing agents, shampoos, emulsifiers, dispersing agents, flotation aids, softeners, disinfectants and thickeners.

United States Patent Distler et a].

PRODUCTION OF AMMONIUM BETAINES Inventors: Harry Distler, Ludwigshafen; Rudi Widder, Eppelheim, both of Germany Badische Anilin- & Soda-Fabrik Alrtiengesellschaft, I Ludwigshafen/Rhine, Germany Filed: Dec. 8, 1970 Appl. No.: 96,270

Assignee:

US. Cl 260/401, 260/247.1, 260/268 R,

260/293.85, 260/294.8 F, 260/50l.l2, 252/526, 252/DIGL 7 Int. Cl. C07c 143/86 Field of Search 260/40l, 501.12,

Primary Examiner-Alex Mazel Assistant Examiner-Jose Tovar Attorney-Johnston, Root, O'Keeffe, Keil, Thompson & Shurtleff {57] ABSTRACT The production of ammonium betaines by reaction of adducts of an oxide of sulfur and an amine with an aziridine, and the new ammonium betaines themselves. The new. compounds obtainable according to the process of the invention are surfactants, particularly detergents and assistants in the textile field, softeners, washing aftertreatment agents, germicides, and valuable starting materials for the production of detergents, cleaning agents, detergents, wetting agents, textile assistants, dishwashing agents, shampoos, emulsifiers,

dispersing agents, flotation aids, softeners, disinfectants and thicken'ers.

6 Claims, No Drawings general formula:

where the individual radicals R and R may be identidioxide or sulfur trioxide, for example according to the cal or different and each denotes an aliphatic, oycloaliphatic, araliphatic or aromatic radical, R may also each denote a hydrogen atom, both radicals R and R together or one of the radicals R and R together with the adjacent nitrogen atom may also be members of a heterocyclic ring, R" denotes a hydrogen atom or an aliphatic radical and X denotes the radical SO or -SO are obtained advantageously by reacting an adduct of an oxide of sulfur and an amine having the general formula:

irm X(-) in which R, R and X have the meanings given above with an aziridine having the general formula:

CH: '(III) l (HI -N (Ill -CH N sor I u x u l til; (flit-"N l u u l our N 0, our-N sor The process according to the invention gives a large number of ammonium sulfamatobetaines and ammonium thionomatobetaines in a simple way in good yields and high purity.

The adducts used as starting material II are generally .prepared by reaction of appropriate amines with sulfur method described in German published Patent Application P 19 36 789.6) and in HoubenWeyl,

Methoden der organischen Chemie", volume Vl/2, pages 455 to 457and volume 9, pages 503 et seq. Substances, for example appropriate thionyl diarrimonium sulfites prepared by reaction of tertiary amines with sulfur dioxide,-which form starting materials ll under the reaction conditions may be used instead of starting materials II.

Preferred starting materials [I and consequently preferred end products I are those inwhose formulae the individual radicals R and R are identical or different and each denotes alkyl having from 1 to 25, preferably from 2 to 18, carbon atoms, alkenyl or alkynyl having in each case from 2 to 25, preferably from 2 to 18, carbon atoms (the carbon chain of the alkyl, alkenyl and- /or alkynyl radical being interrupted if desired by the groups -CO--NH- and/or cycloalkyl having 5 to 12 carbon atoms, aralkyl having 7 to 12 carbon atoms, phenyl or naphthyl, one radical R may also denote hydrogen and both radicals R and R together or one radical R and R together with the adjacent nitrogen atom may also denote members of a five-membered or six-membered heterocyclic ring which may contain (in addition to the nitrogen atom) another nitrogen atom or an oxygen atom, and X de notes the radical SO or SO The said radicals and rings may also bear, as substituents, groups and/or atoms which are inert under the reaction conditions, for example hydroxyl, cyano, sulfonic acid, carboxamido or nitro; fluorine, chlorine or bromine; or carbalkoxy, alkyl, acyloxy, acylamido or alkoxy, in each case having up to four carbon atoms.

When starting from a mixture of amines, for example the mixture of dimethyl palm oil amines (substantially consisting of a nitrogen atom bearing, as substituents,

two methyl groups and a lauryl group) obtained by reaction of dimethylamine with lauryl chloride, corresponding mixtures of adducts II and accordingly mixtures of end products I are obtained. In the case of tertiary polyamines, for example N,N-dimethylpiperazine, the corresponding polyadducts and corresponding polybetaines I are obtained.

The sulfur dioxide or sulfur trioxide adducts of the following bases may be used as starting materials: trimethylamine, triethylamine, tributylamine, triethanolamine, N,N-dimethyl-N-hexylamine, N,N-dimethyl-N' octylamine, N.N-dimethyl-N-decylamine, N,N-dimeth- I yl-N-tridecylamine, N,N-dimethyl-N-octadecylamine,

N-methyl-N,N-dioctadecylamine, tridodecylamine, tri- 3 N-methyl-N-ethyl-N-phenylamine,

dimethyl-N-(,B-lauratoethyl)-amine, N,N-dimethyl-N- (,B-oleatoethyD-amine, N,N-dimethyl-N-('y-stearoylamidopropyl)-amine; similarly substituted primary and secondary amines; pyridine, N-ethylimidazole, N- methylethylenimine, N-methylmorpholine, N- methylpiperidine, N-octylpiperidine, N-

3 decylpiperidine, N-tridecylpiperidine, N- octadecylpiperidine, and N,N-dimethyl-(y-perquently preferred end products 1 are those in whose formulae R denotes hydrogen or alkyl having one to four carbon atoms. Examples are ethylenimine, N- methylimine, N-isopropyliminc and N-tertbutylethylenimine.

The reaction is carried out as a rule at a temperature of from to +150C, preferably from 20 to 100C, at atmospheric or superatmospheric pressure, continuously or batchwise. It is convenient to use organic sol- 1 vents which are inert under the reaction conditions, for example ethylene chloride, chloroform, trichloroethylene; aromatic hydrocarbons, for example benzene; ethers, for example dioxane, tetrahydrofuran or diethyl ether; aliphatic hydrocarbons, for example heptane, octane, petroleum ether or ligrion; preferably ketones, for example methyl ethyl ketone and particularly acetone; or appropriate mixtures.

The reaction may for example be carried out as follows: Starting material 111 is slowly fed into starting material 11, which may contain a solvent, while mixing well. The mixture is then kept at the reaction temperatures for from half an hour to five hours. The end product is separated by a conventional method, for example by filtration or by removal of the solvent and recrystallization ofthe residue from a suitable solvent, for example ethanol, methanol, ethyl acetate, acetone or mixtures of the same.

In a preferred embodiment of the process according to the invention the amine is first placed in a vessel at a low temperature within the said range of reaction temperatures and the sulfur oxide is slowly added with good mixing. Starting material 111 is then added to the adduct thus formed at the same temperature or at a higher temperature and the reaction is carried out in the way described above. Similarly theamine, sulfur oxide, aziridine Ill and, if desired, a solvent may be mixed with each other and reacted under the reaction conditions. The end product I may thus be prepared economically in a one-stage process using readily accessible starting materials.

Compounds which can be prepared by the process according to the invention are surfactants, particularly detergents and assistants in the textile industry, softeners, washing aftertreatment agents, germicides and valuable starting materials for the production of detergents, cleaning agcnts, wetting agents, textile assistants,

dishwashing agents, shampoos, emulsifiers, dispersing agents, flotation aids, softeners, disinfectants and thickeners.

For example a good wetting effect on cellulose material is obtained with N-dimethyl-N-dodecyl-N-B- sulfamidoethylammonium betaine in a concentration of only 1 to parts in 100 parts of water. A mixture of N-pentadecyl-flthionamidoethylammoniurn betaine and N-hexadecyl-B-thionamidoethylammonium betaine may be used in a moderate lather dishwashing agent having for example the following composition:

5 parts of diethanolamine alkylbenzenesulfonate 5 parts of nonylphenyl.l0 ethylene oxide 5 parts of a mixture of N-pentadecyl-fl-thionamidoethylammonium betaine and N-hexadecyLB- thionamidoethylammonium betaine 5 parts of isopropanol 1 5 5 parts of tetrapotassium pyrophosphate and 75 parts of water.

The following mixture is suitable for example for tex- A tile finishing in organic solvents:

90 parts of 1,1,l-trichloroethane 5 parts of water and v 5 parts of N-methyl-bis-(N-stearoylamidopropyl)-N- B-sulfamido-ethylammonium betaine.

The end products may also be used as emulsifiers in the copolymerization of polymerizable monomers, for example vinyl homologs. For example very stable dis-, persions are obtained when polymerization is carried out as follows: A mixture of 1,500 parts of water, 45 parts of N-dimethyl-N-dodecyl-N-B- sulfitoamidoammonium betaine, parts of an adduct prepared by a conventional method from n-dodecyl alcohol and ethylene oxide in the molar ratio 1 25, 45 parts of N-vinyl-N-methylimidazolium methosulfate, 30 parts of 30 percent hydrogen peroxide, 1200 parts of vinylidene chloride and 300 parts of ethyl acrylate is polymerized while stirring at 50 to 60C in a polymerizer. Polymerization is over after eight hours. An about 50 percent dispersion of a copolymer of vinylidene chloride and ethyl acrylate is obtained which is stable in storage and devoid of coagulate. The K value of the copolymer is 60 measured in 0.5 percent solution in cyclohexanone. The dispersion does not froth at pH 7. The dispersion is suitable as a primer for coating film.

The following Examples illustrate the invention. The parts specified in the following Examples are by weight.

EXAMPLE 1 One hundred parts of ethylene chloride and 50 parts of dioxane are cooled to 0C in a stirred vessel. Twenty parts of liquid sulfur trioxide is slowly added in about twenty minutes at 0C while stirring well. A solid (a complex of dioxane and S0 is deposited in crystalline form. 170 parts of N-methyl-bis-(N- stearoylamidopropyl)-amine dissolved in 250 parts of ethylene chloride is slowly added in 30 minutes at to C to the suspension. Then 12 parts of ethylenimine is added. The mixture is heated to to C and stirred for about 4 hours at this temperature. The solvent is then removed at subatmospheric pressure. Two hundred parts of N-methyl-bis-(N- stearoylamidopropyl) NB-sulfamidoethylammonium betaine is obtained as a colorless solid powder. It has a sintering point of to 165C.

EXAMPLE 2 Three hundred thirty-nine parts of N-methyl-bis-(N- stearoylamidopropyl)-amine is dissolved in 600 parts of ethylene chloride at 60C in a stirred vessel. The whole is cooled to 20C to 25C and a solution of 40 parts of sulfur trioxide in 80 parts of ethylene chloride is added slowly within about 30 minutes. The mixture is stirred for 1 hour and 22 parts of ethylenimine is slowly added at this temperature. The whole is heated to 60 C and stirred for another 4 hours. The solvent is removed at subatmospheric pressure. Three hundred ninety-five parts of N-methy1bis-(N-stearoylamidopropyl)-N-B- sulfamidoethylammonium betaine is obtained as a co1- orless solid powderwhich can be emulsified in water to give a clear product. It has a sintering point of about 165C.

EXAMPLE 3 A solution of a mixture of 63.5 parts of N -methyl-N- bis-hexadecylamine and lfJ- methyl-N-bisoctadecylamine in 101 parts ofethylene chloride is slowly added in about thirty minutes at from to 20C EXAMPLE 4 a. A solution of 62 parts of methylamine in 200 parts of acetone is slowly added at 5C to 0C While-stirring to a solution of I28 parts of sulfur'dioxide in 300 parts of acetone. The mixture is stirred for another hour and the precipitated methylthionamicacid {306 parts) is suction filtered and washed with acetone. It has a melting point of 96 to 98C.

b. 21.5 parts of ethylenimine is slowly added at 30 to 40C to a solution of 92.5 parts of methylthionamic acid in 150 parts of ethanol. After the whole, has been stirred for another two hours, the solvent is distilled off at subatmospheric pressure and 102. parts (89.4 percent of the theory) of N-methyl-N-fi-thi gnamidoethylammonium betaine is obtainedfas ayellowviscous oil. 11, 1.4949.

EXAMPLE 5 Thirty-two parts of sulfur dioxide is passed into a solution of 36.5 parts of butylamine in 150 parts of benzene at to C. 2 l .5 parts of ethylenimine is slowly added at to C to this solution of butylthionamic acid. A brown crystallizing solid is obtained which is suction filtered from the benzene. The residue is taken up in ethanol, allowed to crystallize out and auction filtered. 57 parts (63.3 percent of the theory) of N-butyl- B-thionamidoethylammonium betaine is obtained. Melting point 230C with decomposition.

' EXAMPLE 6 Thirty-two parts of sulfur dioxide is passed into 127 parts ofa mixture of pentadecylamine and hexadecylamine at 30C. The whole is stirred for another 2 hours. 21.5 parts of ethylenimine is then slowly added at 25C. 173.2.parrs (96.0 percent of the theory) of a mixture of N-pentadecyl-B-thionamidoethylammoniurn betaine 6 I N-stearyl-N-B-thionamidoethyl-ammonium having a melting point of from 164 to 167C EXAMPLE 8.

a. A solution of 64 parts of sulfur dioxide in 150 parts of acetone'is added to a solution of 267 parts of oleylamine in 400 parts of acetone while stirring at 5C. The whole is stirred for another hour and the precipitated solid is filtered off and'washed with acetone; Three betaine hundred twenty-one parts (94.0 percent of the theory) of oleylthionamic acid is obtained. The melting point is 78 to 80C.

b. 8.6 parts of ethylenimine is slowly added to a solution of 66 parts of oleylthionamicacid in 'IOOp'arts of ethanol. The whole is stirred for another 2 hours and the solvent is distilled off at subatmospheric pressure. Sixty-five parts (87.3 percent of the theory)'of N-oleyl- N-B-thionamidoethylammonium betaine is obtained in the form of a viscous yellow paste. u 1.4820.

EXAMPLE 9 a. A solution of 46.5 parts of aniline in 150 parts of acetone is slowly added to a solution of32 parts of sulfur dioxide in 250parts of acetone at -5C-and the mixture is stirred for another half an hour. The precipitated solid is suction filtered and dried.-67.2 parts (85.5 per'-' and N-hexadecyl-B-thionamidoethylammonium betaine is obtained as a brown paste. 12); 1.4736.

E AMPLE 7 Sixteen parts of sulfur dioxide is passed into a solution of 67 parts of stearylamine in 250 parts of benzene at 50C while stirring. The whole is stirred for another two hours and then 1 1 parts of ethylenimine is added slowly to this solution. A brown solid is precipitated which is filtered off and recrystallized from alcohol. The yield is 85.2 parts (80.1 percent of the theory) of cent'of the theory) of phenylthionamic acid'is-obtained in the form of colorless crystals. The melting point'is 74 to 77C. Y

b. 8.6 parts of ethylenimine is slowly added to a solu tion of 31.4 parts of phenylthionamicacidin 150 parts of ethanol while stirring at 25C. The whole is stirred for another hour. The solvent is-distilled off at subatmospheric pressure. 37 parts (98.5'percent of the theory) of N-phenyl-N-B-thionamidoethylammonium betaine is obtained as a yellow oil. 12,, 1.5307.

7 7 EXAMPLE 10 a. A solution of parts of dimethylamine in parts of acetone is slowly addedto a solution of' 128 parts of sulfur dioxide in 200 parts of acetone. The mix ture is stirred for another hour and the colorlesssolid formed is suction filtered. 198 parts (90.7 percent of" the theory) of dimethyl'thionamic acid is obtained in I the form of colorless very hygroscopic crystals. The

melting point is 85 to 88C. I

b. 54.5 parts of dimethylthionamic acid is dissolved hot in 150 parts of ethanol. 21.5 parts of ethylenimine is added to this solution at 40C. The whole is stirred for another 2 hours. The ethanol is distilled off at subat-' mospheric pressure. 67 parts (88.2 percent of the the ory) of N,N-dimethyl-N-B-thionamidoethylammonium betaine is obtained as yellowish crystals. The melting point is 74 to 75C. I a

p XAM 11 a. Seventy-three'parts ofdiethylamine'in 1.50 parts of acetone is slowly added to a solution of 64 parts of sul-f fur dioxide in 200 parts of acetone at 0 to +5C while" stirring. The whole is stirred for another hour. A brown solid is obtained which is suction filtered and washed with acetone. The yield is 109 parts (79.5 percent of the theory) of diethylthionamic acid (melting point 98 to 99C).'

b. 2L5 parts of ethylenimine is slowly added-to a so-." lution of 68.5 parts of diethyl thionamic acid in 200 parts of ethanol. The mixture is stirred for another two.

hours. The ethanol. is distilled off at subatmospheric pressure; Fifty parts (48.0 percent of the theory) of N,- N-diethyl-N43-thionamidoethylammonium betaine is obtained in the form of colorless very hygroscopic crystals.

EXAMPLE 12 a. A solution of 85 parts of piperidine in 100 parts of acetone is slowly added to a solution of 64 parts of sulfur dioxide in 200 parts of acetone. The deposited col- EXAMPLE 13 a. Sixty-four parts of sulfur dioxide is passed into a solution of 87 parts of morpholine in 150 parts of benzene at 30C. The whole is stirred for another 2 hours at 25C and the benzene is distilled off at,subatmospheric pressure. The crystalline residue is recrystallized from 150 parts of dioxane. One hundred thirtyseven parts of morpholinethionamic acid is obtained (90.7 percent of the theory).

b. 17.2 parts of ethylenimine is slowly added at 25 to 30C to a solution of 60.4 parts of morpholinethionamic acid in 100 parts of ethanol. The whole is stirred for another two hours and then the ethanol is distilled off at subatmospheric pressure. Seventy-five parts (96.1 percent of the theory) of N-B-thionamidoethylmorpholinium betaine is obtained in the form of a colorless viscous oil. 11,, 1.4994.

EXAMPLE 14 a. Thirty parts of trimethylamine is added to.64 parts of liquid sulfur dioxide at 40 to --20C. The mixture is stirred for another 4 hours at 20 to C. The crystalline solid formed is filtered off. 55 parts (88.7 percent of the theory) of thionyldi-(trimethylammonium) sulfite is obtained. Melting point 55C.

CH3 a SOT EXAMPLE 1s Thirty-two parts of sulfur dioxide is passed into a solution of 50.5 parts oftriethylamine in 150 parts of benzene at 20 to 25C while stirring. After the whole has been further stirred for 2 hours. 21.5 parts of ethylenimine is slowly added at 50C. The linear solidformed is filtered off and recrystallized from methanol. The

yield is parts (48.1 percent of the theory) of N- triethyl-N-B-thionamidoethylammonium betaine. The melting point is 148C with decomposition.

EXAMPLE 16 a. Two hundred parts of sulfur dioxide is passed into a solution of 426 parts of N-dimethyldodecylamine in 250 parts of acetone at 20C. The whole is stirred for another three hours at 25C. The solvent is then distilled off at subatmospheric pressure. Five hundred twenty parts (94.0 percent of the theory) of thionyldi- (dimethyldodecylammonium) sulfite is obtained in the form of a yellow oil. 11,, 1.4729.

b. 12.9 parts of ethylenimine is slowly added at 25C to 41 parts of thionyldi-(dimethyldodecylammonium) sulfite while stirring. After further stirring for another three hours at 30 to 35C, 46 parts (85.1 percent of the theory) of N-dimethyl-N-dodecyl-N-B-sulfitamidoethylammonium betaine is obtained in the form of a brownish hygroscopic paste. 11,, 1.4770.

We claim? 1. An ammonium betaine having the formula:

O stearoylamidopropyl, R denotes methyl and X denotes 2. An ammonium betaine having the formula:

in which R and R are y-stearoylamidopropyl, B-lauroyl-amidoethyl, 'y-lauroylamidopropyl, y-perfluorocaprylamidopropyl or methyl, at least one of R and R being other than methyl, and X denotes -SO;,.

3. A process for the production of an ammonium betaine having the formula:

in which R and R are y-stearoylamidopropyl, B-lauroyl-amidoethyl, y-lauroylamidopropyl, y-perfluorocaprylamidopropyl or methyl. at least one of R and R being other than methyl. and X denotes SO which comprises reacting ethylenimine with an adduct of sulfur trioxide and an amine having the formula in which R, R and X have the meanings given above at a molar ratio of said ethylenimine to said admethyl. 

2. An ammonium betaine having the formula:
 3. A process for the production of an ammonium betaine having the formula:
 4. A process as claimed in claim 3, said temperature being in the range of 20* to 100*C.
 5. A process as claimed in claim 3 wherein the reaction of said ethylenimine and said adduct is carried out in an organic solvent which is inert under the reaction conditions.
 6. A process as claimed in claim 3 wherein both radicals R1 denote gamma -stearoylamidopropyl and R2 denotes methyl. 